Process for breaking emulsions of the oil-in-water class



Patented Mar. 11, 1952 NEED STATES PROCESS FOR BREAKING slvro sroNs OF THE OIL-IN-WATER CLASS Louis T. Monson, Puente, Califi, assignor to Petrolite Corporation, Ltd., Wilmington, DeL, a

corporation of Delaware This invention relates to a process for resolving or separating emulsions of the oil-in-Water class, by subjecting the emulsion to the action of certain chemical reagents.

Emulsions of the oil-in-water class comprise organic oily materials, which, although immiscible with water or aqueous or non-oily media, are distributed or dispersed as small drops throughout a continuous body of non-oily medium. The proportion of dispersed oily material is in many and possibly most cases a minor one.

Oil-field emulsions containing small proportions of crude petroleum oil relatively stably dispersed in water or brine are representative oil-in- Water emulsions. Other oil-in-water emulsions include: stem cylinder emulsions, in which traces of lubricating oil are found dispersed in condensed steam from steam engines and steam pumps; Wax hexane water emulsions, encountered in de-waxing operations in oil refining; butadiene tarin-water emulsions, in the manufacture of butadiene from heavy naphtha by cracking in gas generators, and occurring particularly in the wash box waters of suchsystems; emulsions of flux oil in steam condensate produced in the catalytic dehydrogenation of butyl ene to produce butadiene; styrene-in-water emulsions, in synthetic rubber plants; synthetic latexin-water emulsions, in plants producing co-polymer butadiene-styrene or GRS synthetic rubber; oil-in-water emulsions occurring in the cooling water systems of gasoline absorption plants; pipe press emulsions from steam-actuated presses in clay pipe manufacture; emulsions of petroleum residues-in-diethylene glycol, in the dehydration of natural gas.

In other industries and arts, emulsions of oily materials in water or other non-oily media are encountered, for example, in sewage disposal operations, synthetic resin emulsion paint formulation, milk and mayonnaise processing, marine ballast water disposal, and furniture polish formulation. In cleaning the equipment used in processing such products, diluted oil-in-water emulsions are inadvertently, incidentally, or aco'identally produced. The disposal of aqueous wastes is, in general, hampered by the presence of oil-in-water emulsions.

Essential oils comprise non-saponifiabl'e materials like terpenes, lactones, and alcohols. They also contain saponifiable" esters or mixtures of saponifiable and non-saponifiable materials. Steam distillation and other production procedures sometimes cause oil-in-water emulsions 2 V to be produced, from which the valuable essential oils aredifficultly recoverable.

In' all such examples, a non-aqueous or oily material is emulsified in an aqueous or non-oily material'with which it is naturally immiscible. The term oil is used herein to cover broadly the water-immiscible materials present as dispersed particles in such systems. The non-oily phase obviously includes diethylene glycol, aqueous solutions, and other non-oily media in addition to water itself.

The foregoing examples illustrate the fact that, within the broad genus of oil-in-water emulsions, there are at least three important sub-genera. In these, the dispersed oily material is respectively non-saponifiable, saponifiable, and a mixture of non-saponifiable and saponifiable materials. Among the most important emulsions ofnon-saponifiable material in water are petroleum oil-in-water emulsions. Saponifiable oilin-water emulsions have dispersed phases comprising, for example, saponifiable oils and fats and fatty acids, and other saponifiable oily or fatty esters and the organic components of such esters to the extent such components are immiscible with aqueous media. Emulsions produced from certain blended lubricating compositions containingboth mineral and fatty oil ingredients are examples of the third sub-genus.

Oil-in water emulsions contain widely different proportions of dispersed phase. Where the emulsion isa waste product resulting from the flushing with water of manufacturing areas or equipment, the oil content may be only a few parts per million. Resin emulsions paints, as produced, contain a major proportion of dispersed phase. Naturally-occurring oil-field emulsions of the oil-in-Water class carry crude oil in proportions varying from a few parts per million to about 2'0 or even higher in rare cases.

The present invention is concerned with the resolution of those emuisions of the oil-in-water class which contain a minor proportion of dispersed phase, ranging from 20% down' to' a few parts per million. Emulsions containing more than about 20% of dispersed phase are commonlyofsu'ch' stability as to beless responsive to the presently disclosed reagents, possibly because of the appreciable content of emulsifying agent present in such systems, whether intentionally incorporated for the purpose of stabilizing them or not. 7

Although the present invention relates toemulsions containing as much as 20% dispersed oily material, many if not most of them contain appreciably less than this proportion of dispersed phase. In fact, most of the emulsions encountered in the development of this invention have contained about 1% or less of dispersed phase. It is to such oil-in-water emulsions having dispersed phase volumes of the order of 1% or less to which the present process is particularly directed. This does not mean that any sharp line of demarcation exists, and that, for example, an emulsion containing 1.0% of dispersed phase will respond to the process, whereas one containing 1.1 of the same dispersed phase will remain unaffected; but that, in general, dispersed phase proportions of the order of 1% or less appear most favorable for application of the present process.

In emulsions having high proportions of dispersed phase, appreciable amounts of some emulsifying agent are probably present, to account for their stability. In the case of more dilute emulsions, containing 1% or less of dispersed phase, there may be difiiculty in accounting for their stability on the basis of the presence of an emulsifying agent in the conventional sense. For example, steam condensate frequently contains very small proportions of refined petroleum lubricating oil in extremely stable dispersion; yet neither the steam condensate nor the refined hydrocarbon oil would appear to contain anything suitable to stabilize the emulsion. In such cases, emulsion'stability must probably bepredicated on some basis other than the presence of an emulsifying agent.

The present process, as stated above, appears to be effective in resolving emulsions containing up to about 20% of dispersed phase. It is particularly effective on emulsions containing not more than 1% of dispersed phase, which emulsions are the most important, in view of their common occurrence.

The present process is not believed to depend for its effectiveness on the application of any simple laws, because it has a high level of effectiveness when used to resolve emulsions of widely v different composition, e. g., crude or refined petroleum in water or diethylene glycol, as well as emulsions of oily materials like animal or vegetable oils or synthetic oily materials in water.

Some emulsions are by-products of manufacturing procedures in which the composition of the emulsion and its ingredients is known. In many instances, however, the emulsions to be resolved are either naturally-occurring or are accidentally or unintentionally produced; or in any event they do not result from a deliberate or premeditated emulsification procedure. In numerous instances, the emulsifying agent is unknown; and as a matter of fact an emulsifying agent, in the conventional sense, may be felt to be absent. It is obviously very difiicult or even impossible to recommend a resolution procedure for the treatment of such latter emulsions, on the basis of theoretical knowledge. Many of the most important applications of the present process are concerned with the resolution of emulsions which are either naturally-occurring or are accidentally, unintentionally, or unavoidably produced. Such emulsions are commonly of the most dilute type, containing about 1% or less of dispersed phase, although concentrations up to 20% are herein included, as stated above.

The process which constitutes the present invention consists in subjecting an emulsion of the oil-in-water class to the action of a reagent or demulsifier of the kind subsequently described, thereby causing the oil particles in the emulsion to coalesce suiiiciently to rise to the surface of the non-oily layer (or settle to the bottom, if the oil density is greater), when the mixture is allowed to stand in the quiescent state after treatment with the reagent or demulsifier.

Reference is made to my co-pending applications, Serial Nos. 181,698 and 181,699, both filed of even date, which relate to processes for the same purpose as that of the present application and which employ reagents related to the present reagents.

Applicability of the present process can be readily determined by direct trial on any emulsion, without reference to theoretical considerations. This fact facilitates its application to naturally-occurring emulsions, and to emulsions accidentally, unintentionally, or unavoidably produced; since no laboratory experimentation, to discover the nature of the emulsion com ponents or of the emulsifying agent, is required.

The reagents employed as the demulsifiers in my process include reaction products produced by the reaction of a polyhalogenated, noninonized organic compound and a surface-active poly-amino condensation polymer, which latter material is, in turn, obtained by the heatpolymerization of a tertiary amino-alcohol of the formula:

[noarommli in which formula, OR is an alkylene oxide radical having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals, glycide radicals, and methylglycide radicals; R1 is a non-aromatic radical having 6 carbon atoms or less; m represents a number varying from 0 to 3; n represents the numeral 1, 2, or 3; and n represents the numeral 0, 1, or 2, with the proviso that n+n'=3; said reaction resulting in the conversion, per molecule of poly-halogenated reactant, of one or more halogen atoms from co-valent to electro-valent state. The heat-polymerized aminoalcohol, in monomeric form, is a tertiary amine containing at least one alkanol or hydroxyalkyl radical.

Such poly-amino reactants may be obtained, for example, by the polymerization of triethanolamine, tripropanolamine, or the like, in such manner as to eliminate Water and produce ether linkages. Such polymers may, in some cases, consist of dimers; but trimers, tetramers, or more highly polymerized forms, up to octamers or higher, are useful reactants here. They are characterized by being surface-active, which means that their dilute solutions foam, reduce the surface tension of water, act as emulsifiers, etc. Their exact composition cannot, in all cases, be depicted by the usual chemical formulas, because they are poly-functional, they may be acyclic or alicyclic, and they are subject to wide variations. The primary reaction is undoubtedly etherization. However, if some secondary amine, as, for example, diethanolamine or dipropanolamine, is present, water may be eliminated by some reaction other than etherization, with the result that 2 nitrogen atoms are united by an alkylene radical, as distinguished from an alkylenoxyalkylene radical.

Even though the exact structure of the surface-active heat-polymerized alkanolamines herein employed as reactants is not fully understood, their method ofmanufacture is wellknown, and they are used commercially for various purposes. The following description is typical of the conventional polymers.

The tertiary alkanolamines having a single nitrogen atom, i. e., monoamines, may be looked upon in simplest aspect as oxyalkylated deriyatives of ammonia. For example, although triethanolamine may be manufactured invarious ways, it can be made by treating one mole of ammonia with 3 moles of ethylene oxide. Analogues may be prepared by using other alkylene oxides containing a reactive ethylene oxide ring, as, for example, propylene oxide, butylene oxide, glycide or methylglycide, or mixtures of these various alkylene oxides. Such products need not be derived directly from ammonia, but may be derived from primary amines containing a radical having 6 carbon atoms or less, such as methylamine, ethylamine, propylamine, butylamine, amylamine, and hexylamine. For the present purpose, I specify that any such radical present shall be non-aromatic. Aromatic radicals, if present, undesirably reduce the basic character of the amine.

If a product like triethanolamine is treated with an excess of an oxyethylating. agent like ethylene oxide, one introduces the oxyethylene radical between a terminal hydrogen atom and the adjacent oxygen atom. Thus, ether-aminoalcohols obtained by reacting triethanolamine or tripropanolamine with one or two or even as many as 9 moles of ethylene oxide are well known. The other similar ether-aminoalcohols are derived in the same manner and require no further description. For purposes of clarity, the tertiary amines herein included as raw materials for the polymerization step may be summarized by the following formula:

wherein OR is an alkylene oxide radical having 4 carbon atoms or less and preferably is the ethylene oxide radical, As indicated, OR may be the propylene oxide radical, the butylene oxide radical, the glycide radical, or the methylglycide radical; R1 is a non-aromatic radical having 6 carbon atoms or less; 121. represents a numeral varying from 0 to 3; n represents the numeral 1, 2, or 3; and n represents the numeral 0, 1, or 2, with the proviso that n+11/=3.

I prefer to use triethanolamine as my amino raw material. While the commercial product contains moderate amounts of diand monoethanolamine, I have found it suitable.

It will be pointed out subsequently that the temperatures employed for polymerization are commonly in the neighborhood of 250 C. This means that, in most instances, much of any monoor diethanolamine originally, present may be volatilized and lost before having had an opportunity to react. I have found no important difference between polymers produced from chemically pure triethanolamine and those produced from commercial. triethanolamine having minor percentages of monoand diethanolamine present.

The poly-amino products obtained in the mam ner herein described, when manufactured in),

iron vessels, are viscous, deep-amber-coloredqto;

dark brown products. The degree of polymerization may be estimated approximately by the loss of water and the increase in viscosity. However, it is better to make an actual molecular weight determination in the usual manner, for example, cryoscopically. The dimers as a class show some surface-activity; if the product is heated further, with further loss of water and further increase in viscosity, the degree of polymerization and the level of surface-activity are obviously higher.

Polymerization of the basic hydroxyamines is efiected by heating at elevated temperatures, generally in the neighborhood of 250 0., preferably in the presence of catalysts like sodium hydroxide, potassium hydroxide, sodium ethylate, sodium glycerate, or catalysts of the kind commonly used in the manufacture of superglycerinated fats and the like. The proportion of catalyst employed may vary from about 0.1%, in some instances, to about 1% in others. If the aminoalcohol is low-boiling, precautions must be taken not to lose the material during polymerization. At the same time, water of reaction must be permitted to be removed. At times, the process can be conducted most readily by permitting a portion of the volatile constituents to distill, and subsequently subjecting the vapors to condensation. The condensed distillate contains water formed by the reaction. After removing such water from the distillate, e. g., by distilling with xylene, and separating the xylene, the dried condensate may be returned to the reaction chamber for further processing. Sometimes, condensation is best effected in the presence of a high-boiling solvent, which is permitted to distill in such a manner as to remove the water of reaction. In any event, the rate of reaction and the character of the polymerized product depend not only on the original reactants, but also on the nature and amount of catalyst, the temperature and time of reaction, and the rate of water removal from the combining mass. Polymerization can be effected in absence of catalysts, but the reaction usually takes appreciably longer, sometimes even at higher temperature.

The rate of reaction and the degree of polymerization are affected by the nature of the reaction vessel. In the examples cited below, it is intended that the reaction take place in a metal vessel such as iron. In order to obtain the same degree of polymerization in a glass vessel, the reaction time would usually have to be increased by -400%.

Surface-active, as herein employed and as generally used, refers to compositions which are water-dispersible at least to the extent of producing a colloidal dispersion or sol. Thus, I do not contemplate the use of products obtained by polymerization to the extent that they are no longer dispersible or miscible in Water. In the case of some of my poly-amino reactants, the degree of water-dispersibility and surface-activity is low; but conversion into the final product by reaction with the poly-halogenated reactant results in the formation of a product of desirably enhanced surface-activity.

Suitable amino raw materials, in addition to triethanolamine and tripropanolamine already mentioned, include ethyldiethanolamine, diethylethanolamine, propyldipropanolamine, dipropylpropanolamine, cyclohexyldiethanolamine, cyclohexyldipropanolamine; etc.

CEHlOH canton OH (See U. S. Patent No. 2,290,415, dated July 21, 1942, to De Groote.)

Examples of the preparation of suitable polyamino reactants include the following:

POLY-AMINO REACTAN T Example 1 Add 1% of caustic soda to commercial triethanolamine and heat the mixture for 3 hours at 245-250 C. with constant stirring. Condense any distillate and reserve for re-use after an intermediate re-running dehydration step, as described above. The reaction product is largely dimeric, as shown by molecular weight determination.

POLY-AMINO REACTANT Example 2 Use the procedure and reactants of Poly- Amino Reactant, Example 1, above, but continue the heating for 1.5 hours longer. The reaction mass is largely the trimer, on a statistical basis.

POLY-AMINO REACTAN'I Example 3 Use the procedure and reactants of Poly- Amino Reactant, Examples 1 and 2, above, but continue heating until incipient rubbering at reaction temperature occurs. The product, on the average, has an average molecular weight equivalent to a mixture of tetrameric and pentameric polymers.

POLY-AMINO REACTANT Example 4 Proceed as in Poly-Amino Reactant, Examples 1, 2, and 3, above, except substitute triisopropanolamine for triethanolamine. The reaction proceeds more slowly; and extension of the heating periods to at least twict those specified in those examples is required.

As stated in Poly-Amino Reactant, Example 4, above, triisopropanolamine reacts more slowly than triethanolamine in this heat-polymerization reaction. This may be due to inaccessibility of the OH groups in the branched-chain molecule. subjection of the amine to oxyalkylation, e. g., by reaction with ethylene oxide prior to heat-polymerization, will produce an etherized alkanolamine which has longer alkanol radicals, more accessible in the heat-polymerization reaction.

POLY-AMINO REACTANT Example 5 React 1 mole of triisopropanolamine with 3 moles of ethylene oxide in an autoclave, using 1% of caustic soda as a catalyst and a temperature of about -165 C. After the pressure in the vessel returns to normal (it will rise immediately after addition of the ethylene oxide to as much as 50 p. s. i. g.; but will fall again as the oxide reacts), raise the temperature to about 250 C. and continue heating for 5, 8 and 10 hours, respectively, to attain 3 different levels of polymerization. (The vessels is left open during the 250 C. heating. This is also true for Examples 6 and '7 below.)

POLY-AMINO REACTANT Example 6 Prepare a polyethanolamine of the formula:

ognloczmon NC H4OC H4OH ozrrloozmon by reacting 1 mole of triethanolamine and 3 moles of ethylene oxide in an autoclave, as just described in Example 5, above. Then heat this product at about 250 C. for 3 hours, 4.5 hours, and to incipient rubbering, as described in Poly- Amino Reactant, Examples 1, 2, and 3, to attain three different levels of heat-polymerization.

POLY-AMINO REACTANT Ezrample 7 Repeat Poly-Amino Reactant, Example 6, except use 9 moles of ethylene oxide and 1 mole of triethanolamine, to produce a polyethanolamine of the formula:

Heat this product at about 250 C. for periods of 3 hours, 4.5 hours, and to incipient rubbering, respectively, as in Poly-Amino Reactant, Examples 1, 2 and 3, to attain three different levels of heat-polymerization.

POLY-AMINO REACTANT Example 8 Prepare a heat-polymerized triethanolamine by following the procedure of Poly-Amino Reactant, Examples 1, 2, or 3. Determine its hydroxyl number. Place the product in an autoclave and introduce ethylene oxide in the ratio of 1 mole for each OH group present, using a temperature of about C. and 1% of caustic soda as a catalyst, as in Example 5, above.

9 POLY-AMINO REACTANT Example 9 Repeat Poly-Amino Reactant, Example 8, but

introduce, respectively, 2 and 3 moles of ethylene oxide for each OH group.

If desired, mixed alkylene oxides may be employed to produce these oxyalkylated amino materials; or such alkylene oxides may be introduced in any desired sequence instead of in admixture. It is apparent that many procedural variations are possible, all of which produce amino bodies of the specified character.

I have found the heat-polymer produced by the simple heating of commercial triethanolamine at about 250 C., with or without catalyst, to be a widely useful poly-amino reactant for producing my finished reagents. I have found that thedimer produced by heat-polymerizing triethanolamine is suitable, especially where the poly-halogenated reactant is of relatively higher molecular weight. I have found that when one approaches pentamers in the heat-polymerization of commercial triethanolamine, one has achieved a relatively high viscosity, approaching rubbering, even at polymerization temperature. My especially preferred poly-amino reactants are, therefore, prepared by heat-polymerizing commercial triethanolamine until the material comprises, on the average, dimers through pentamers. Where one of the radicals linked to the nitrogen atom is, for example, an alkyl radical of 5 or 6 carbon atoms, a substantial plasticizi 1g effect may be observed, which will permit continuing heat-polymerization somewhat further before rubbering occurs. In general, I have found that when the molecular weight of the amino heat-polymer exceeds about 1,000, it often produces an inferior reaction product; and that when it exceeds 2,000, the reaction products produced from it and the poly-halogenated reactants are not particularly effective for the present purpose. I, therefore, disclaim the use of poly-amino reactants of molecular Weight greater than this figure.

My reagents include ingredients which are produced from heat-polymerized tertiary alkanolamines of the kind just described in detail, by reacting them with a wide variety of poly-halogenated non-ionized organic reactants. As the poly-halogenated reactant, I have used, for example, the di-halogenated hydrocarbons such as ethylene dichloride, ethylene dibromide, propylene dichloride, propylene dibromide, butylene dichloride (crude dichlorobutenes), dichloropentanes (mixed dichloro derivatives of normaland isopentane) etc. I have used tri-halogenated hydrocarbon reactants, including chloroform, trichloroethane, trichloroethylene, trichloropropane, etc. Among tetra-halogenated reactants I have used are carbon tetrachloride and tetrachloroethane.

Halogenated reactants containing more than 4 halogen atoms in the molecule are likewise useful reactants for the present purpose. For example, paraffin may be chlorinated to introduce large proportions of that element. Commercially these are offered by Hooker Electrochemical Corporation, as, for example, GP 40, CP 50, and CP 70, the designations being understood to mean chlorinated paraflin, approximately 40% chlorine content, etc. The actual chlorine contents of such products are quite close to the percentages suggested by such designations. The product CP 40, for example, contains about 42% 10 chlorine, equivalent to about 7.5 atoms of chlorine per molecule. CP contains about 9 atoms of chlorine per molecule; and CP contains about 21 atoms of chlorine per molecule. All these products are useful reactants here.

The poly-halogenated reactant need not be a halogenated hydrocarbon, however. Very good results have been obtained from products obtained from dichloromethyl ether, dichloroethyl ether, dichloroisopropyl ether, a mixture of dichloroethyl ether and dichloroisopropyl ether (available under the tradename Betachlor from Wyandotte Chemical Corporation), dibromoethyl ether, glycerol dichlorohydrin, triglycol dichloride, etc.

A convenient means for preparing other polyhalcgenated reactants suitable for the present purpose is afforded by epichlorohydrin. By introducing at least 2 moles of this compound into each molecule of a poly-hydrox'ylated body like glycerol, diglycerol, ethylene glycol, polyalkyleneglycols, oxyalkylated glycerol, erythritol, pntaerythritol, etc., useful poly-halogenated reactants may be prepared. The following examples illustrate this point:

POLY-HALOGENATED REACTANT Example 1 Glycerol (1 mole) is mixed with 1% of stannic chloride and reacted with 3 moles of epiohlorohydrin. The reaction evolves heat and should be conducted cautiously at minimum temperature. A temperature of less than C. sufiices. The roduct is a tri-chloro reactant suitable for the present purpose.

POLY-HALOGENATED REACTANT Example 2 Glycerol (1 mole) is reacted with 3 moles of ethylene oxide in an autoclave, using 1% caustic soda as catalyst and a temperature of about C. The product is neutralized, 1% stannic chloride is added, and 3 moles of epichlorohydrin are introduced, at about 90 C., as in Poly-Halogenated Reactant, Example 1, above.

POLY-HALOGENATED REACTANT Example 3 Substitute erythritol for glycerol in Poly-Halogenated Reactant, Examples 1 and 2, just above.

Other examples could be recited, showing the use of diglycerol, ethylene glycol, polyethylene glycols, polypropylene glycols, etc., as starting materials which can be converted through the medium of epichlorohydrin into poly-halogenated reactants useful in producing ingredients of my finished reagents. The foregoing examples suffice to illustrate but obviously do not exhaust the field of useful poly-halogenated reactants.

I specifically include poly-iodo and poly-fluoro compounds among my class of poly-halogenated reactants.

I exclude from my class of useful poly-halogenated reactants ionizable poly-halogenated organic compounds such as dichloroacetic acid and trichloroacetic acid.

I likewise exclude poly-halogenated aromatic compounds wherein the halogen atoms are attached directly to the aromatic ring. Use of such reactants would result in the presence, in the finished ingredient of my product, of an aromatic ring directly linked to nitrogen; this I have found undesirable. Among such aromatic poly-halogenated materials specifically excluded is di- 11 chlorobenzene. Dichlorobenzoic acid is excluded, both for the reason that it has halogen attached directly to the ring and also because it is ionizable.

To prepare the present class of ingredients of my finished reagents, one need only react one or more members of my class of poly-amino reactants with one or more members of my class of poly-halogenated reactants at a suitable temperature, and in suitable proportions, for a suitable time, as explained below. The temperature required in any case should be determined cautiously, as the reaction involved is usually exothermic, and the mass may react too vigorausly, with production of a rubbery or even somewhat pyrolized material of little utility. For example, when dichloroethyl ether and heat-polymerized triethanolamine are reacted, a temperature of about 110 C. is required; but if the temperature exceeds about 125 0., it is usually unconarollable, and the batch may be spoiled for the present purpose, quickly going to a rubbery stage.

The simplest way to follow the course of the reaction between my poly-amino reactants and my poly-halogenated reactants is based on the fact that, as the reaction proceeds, halogen atoms which were originally present in un- .onized or co-valent form are converted to ionic )1 electro-valent halogen atoms. Determination )f ionic halogen is, of course, a simple analytical procedure, requiring only titration with silver iitrate.

If one starts with a di-amino reactant and a ii-halogenated reactant, for example, and deter.- nines by analysis of samples taken dm'ing the :ourse of the reaction that one-half or less of ;he halogen present has been converted from the :o-valent or un-ionized state to the electroalent or ionized state, one of the two halogens )riginally present has been reacted, but the sec- )nd remains unreacted. As heating is continued, more and more of the halogen content is conrerted to the ionized state.

It is usually possible to convert all the halogen aresent, unless there is an excess of the halogenated reactant. For example, if a di-amino 'eactant and a di-halogenated reactant are used 11 molal proportions or in proportions where ;here is a deficiency of the halogenated material, he proportion of ionic halogen increases as the 'eaction is continued. Substantially complete :onversion of halogen from the un-ionized to onized state is accomplished. Where a di-amino 'eactant and a tri-halogenated reactant are used, )bviously the last one of the three halogen atoms vill not be converted; and substantially com- )lete reaction is indicated by conversion of twohirds of the original halogen. If, on the other land, a tri-amino reactant and a di-halogenated 'eactant are used, the conversion of halogen is omewhat more readily accomplished.

In general, in preparing these ingredients of my reagents, I prefer to have present a molal :xcess of the amino reactant, and to control by malysis the degree of conversion of halogen ttoms from the un-ionized or co-valent state to he ionized or electro-valent state.

While I usually employ a single poly-amino 'eactant and a single poly-halogenated reactant o produce the present class of ingredients of my 'eagents, it is perfectly possible, as stated above, employ a mixture of amino reactants and a nixture of halogenated reactants to produce hem.

In many applications of reagents including ingredients of this general class to the resolution of oil-in-water emulsions, I have ,found it important that not more than one halogen atom per molecule of poly-halogenated reactant be converted in this reaction. One possible explana tion of this fact is that, under such circum stances, there can be no bridging or cross-link ing of the amino molecules. If the amino reactant is relatively large in size, and if crosslinking occurs, the resultant molecule will be of more than double this size. If cross-linking can be avoided, by insuring that not more than one halogen atom is converted, per molecule of polyhalogenated reactant, such excessive size can consequently be avoided.

One phase of my present invention is therefore concerned with the use of reagents including those reaction products of my poly-amino reactants and my poly-halogenated reactants in which not more than one halogen atom per polyhalogenated reactant molecule has been converted from the co-valent or un-ionized state to the electro-valent or ionized state. Included among typical examples of such ingredients of my products are:

REACTION PRODUCT Encample 1 The poly-amino reactant was made from commercial triethanolamine by heating at 250 C. in a steel pot, with stirring, until approximately 30% had been volatilized. The poly-halogenated reactant was dichloroisopropyl ether. A mixture of 310 pounds of the heat-polymerized triethanolamine and. 64 pounds of the halogenated ether was heated in an autoclave for 3.5 hours at C. A sample was withdrawn and analyzed for ionic chlorine by titration with silver nitrate. It was found that 16.5% of the chlorine originally present was then in the ionic state.

REACTION PRODUCT Example 2 The product produced in Reaction Product, Example 1, above, was heated further after adding an additional 6.7 pounds of the poly-halogenated ether. The temperature was maintained at between 128 and 138 C. for 0.5 hours; it was then increased steadily to between 155 C. and 162 C., and held there for 2.5 hours. A sample of the finished product, titrated with silver nitrate as before, showed that 42% of the chlo rine had been converted to the ionic state.

REACTION PRODUCT Example 3 The poly-amino reactant was a heat-polymerized commercial triethanolamine, prepared by heating that material at 255 C. for 12 hours. The poly-halogenated reactant was chloroform. A mixture of 280 pounds of the heat-polymerized triethanolamine and 44.5 pounds of chloroform was heated to C. in the course of 2.5 hours. The pressure reached 40 psig. maximum. A sample withdrawn at that time was titrated with silver nitrate; it showed that 15.9% of the chlorine had been converted to the ionic state.

REACTION PRODUCT Example 4 The heat-polymerized commercial triethanolamine of Reaction Product, Example 3, above, (280 pounds) was mixed with trichloroethylene (50 pounds) and the mixture was heated to 142 C. for 2.5 hours. A sample, analyzed as above, showed 3.8% conversion of the chlorine. Heating was continued for 2 hours, the temperature approximating 160 C. At this point a sample was analyzed; conversion was found to be 9.8% complete. Heating was continued for 2.5 hours longer. At this time, analysis of a sample showed 18.5% of the chlorine present had been converted to the ionic state.

REACTION PRODUCT Example 5 The heat-polymerized commercial triethanolamine of Reaction Product, Example 3, above, (280 pounds) was mixed with ethylene dibromide (66 pounds) and the mixture was heated 2.5 hours at between 155 and 165 C. A sample was analyzed as before, and found to contain approximately 45% of the bromine in the ionic state.

REACTION PRODUCT Example 6 The heat-polymerized commercial triethanolamine of Reaction Product, Example 3, above (280 pounds) was mixed with trichloroethane (50 pounds) and the mixture was heated 7.3 hours. The temperature range was 148-158 C. during this time. Analysis of the product showed that 29% of the chlorine had been converted to the ionic state.

REACTION PRODUCT Example 7 Propylene dibromide (75 pounds) was substituted for ethylene dibromide in Reaction Product, Example 5, above. The mixture was heated 1.5 hours at 156 C. Analysis showed approximately 50% of the bromine had been converted to the ionic state.

REACTION PRODUCT Example 8 Example 9 Commercial triethanolamine (100 parts by weight) was heat-polymerized at 255 C. for 12 hours, with stirring. The temperature was reduced to 110 C. and 19 parts by weight of dichloroethyl ether were introduced. Stirring was continued, the temperature slowly rising to about l-125 C. After 3.5 hours, 43% of the chlorine was found to have been converted to the ionic state. At this point an extremely viscous mass had been produced.

REACTION PRODUCT Example 10 Prepare a heat-polymerized triethanolamine by the procedure of Poly-Amino Reactant, Example 2. Oxyethylate this, using 1 mole of ethylene oxide for each .hydroxyl group present, as determined by Hydroxyl Number determination (e. g., by the Verley-IBiilsing method). Oxyethylation is conducted at about 165 C. in can autoclave, and is complete in about an hour at this temperature. React 280 pounds of this oxyalkylated amino material with '58 pounds of dichloroethyl ether at about C. until titration of a sample with silver nitrate shows that 40% of the chlorine originally present has bee converted to the ionic state.

It is also possible to prepare useful ingredients for my reagents by mixing the poly-halogenated reactant and a simple amino reactant before the latter has been heat-polymerized to produce a poly-amino reactant of the kind described above; and then, by continued heating of the mixture, accomplish simultaneously the reaction between amino body and poly-halogenated body and the heat-polymerization of the former. The following example illustrates this approach.

REACTION PRODUCT Example 11 Commercial triethanolamine (280 pounds) and dichloroethyl ether (53 pounds) are heated in an iron vessel, with stirring, the temperature being held at about -125 C. for 6 hours. The heat was then slowly increased to about 160 C. in 1 hour, then to about 200 C. in another hour, and held there for about 12 hours. In the early stages of the reaction, a granular crystalline product forms; but this slowly decreases in amount as heating continues. The final conversion of chlorine was found to be about 40% to the ionized state.

There are many other occasions when it is found that increasing the molecular size of the reaction product or changing its molecular configuration or both, markedly improves the results obtained when it is used in an oil-in-water demulsifier. For example, if both the polyamino reactant and the poly-halogenated reactant are of relatively low molecular weight, it may be desirable to secure bridging or cross-linking to build a larger and branched molecule of increased effectiveness. In order to accomplish such bridging or cross-linking, at least 2 halogen atoms of the poly-halogenated reactant must be involved in the reaction by which this ingredient is prepared.

A second phase of my present invention is therefore concerned with reagents including those reaction products of my poly-amino reactants and my poly-halogenated reactants in which at least two halogen atoms per poly-halogenated reactant molecule have been converted from the co-valent or un-ionized state to the electro-valent or ionized state. Included among typical examples of such ingredients of my products are:

REACTION PRODUCT Example 12 The poly-amino reactant was a heat-polymerized commercial triethanolamine, prepared by heating that material at 255 Cjfor 12 hours. The poly-halogenated reactant was chloroform. A mixture of 280 pounds of the heat-polymerized triethanolamine and 44.5 pounds of chloroform was heated 8 hours, the temperature averaging about -160" C. most of this time. A sample withdrawn after this time was titrated with silver nitrate and showed 71.7% of the chlorine had been converted to the ionic state.

15 Since 33.3% would represent conversion of 1 chlorine per molecule of chloroform, more than two atoms per molecule had been converted, on a statistical basis, when 71.7% conversion was accomplished, as noted.

REACTION PRODUCT Example 13 The poly-amino reactant of Reaction Product, Example 12, above, (280 pounds) was mixed with 57.5 pounds of carbon tetrachloride. The mixture was heated 2.5 hours, the temperature going as high as 145 C. during this period. Titration of a sample with silver nitrate showed 57.2% of the chlorine had been converted to the ionic state. This is slightly over 2 chlorine atoms per molecule of carbon tetrachloride, on the average. Heating was continued 2.3 hours, and a second sample was titrated with silver nitrate asbefore. It'showed 70.5% conversion of chlorine to the ionic state. Heating was continued for 2.5 hours longer. By the end of the time, 80.1% of the chlorine had been converted to the ionic state.

REACTION PRODUCT Ewample 14 REACTION PRODUCT Example 15 Heat-polymerized commercial triethanolamine (280 pounds) prepared as in Reaction Product, Example 12, and 65.6 pounds of triglyooldichloride were heated for 5.5 hours, the temperature being held at about 165 C. most of this time. Titration with silver nitrate showed 76.3% of the chlorine had been converted to the ionic state. This means that, in about half of the halogenated molecules, both chlorine atoms had been converted.

REACTION PRODUCT Example 16 Mix 280 pounds of heat-polymerized commercial triethanolamine, prepared .as in Reaction Product, Example 12, above, and 63.6 pounds of dichloroisopropyl ether. Heat for 12.5 hours, the temperature usually lying between 160 and 172 C. At the end of this time, the conversion of chlorine from non-ionic to ionic state was substantially complete, as shown by titration with silver nitrate.

C O BQD CT Example 17 Mix 280 pounds of heat-polymerized commercial triethanolamine, prepared as in Reaction Product, Example 12, above, and 53 poundsof the chlorinated paraffin sold by Hooker Electrochemical Company, Niagara Falls, N. Y., under the trade name CP 40. Heat at a temperature not exceeding 200 C. until titration with silver nitrate shows one-third of the chlorine has been 16 converted to the ionic state. (Since the product contains approximately 42.5% chlorine, equivalent to about 7.5 chlorine atoms per molecule, on the average, this degree of conversion is equivalent to the conversion of about 2.5 of the 7.5 chlorine atoms present per molecule.)

REACTION PRODUCT Example 18 Use the poly-amino reactant prepared by heat-polymerizing ethyl diethanolamine at a temperature of 250 C. until determination of the hydroxyl number by the Verley-Bolsing method shows a decline of hydroxyl content to one-half the original value. React the polyamino material, so prepared, 248 pounds, and the p-olychlorinated glycerol material produced in Poly-Halogenated Reactant, Example 1, 60 pounds, at 170 C. until the degree of conversion of the chlorine is found by silver nitrate titration to be two-thirds. (The original chlorine content of the mixture can be determined, for example, by the Parr bomb method for total chlorine.)

REACTION 1 PRODUCT Example 19 Commercial triethanolamine (28.0 pounds) and dichloroethyl ether (53 pounds) were heated in an iron vessel, with stirring, the temperature being held at about -125 C. for 6 hours; at

about for 1 hour; at 200 for another 18' hours. The granular crystalline precipitate which formed in the early stages of the reaction slowly decreased in amount as heating continued. The degree of conversion of chlorine finally achieved was approximately 75%, to the ionized state. (This means that both chlorine atoms of half the dichloroethyl ether molecules had been converted to the ionic state.)

My present reagents include an ingredient of the poly-amino-poly-halogenated reaction product class, just described (irrespective of the degree of conversion of the halogen), plus a multipolar, substantially un-ionized hydrophile colloid, plus an electrolyte of the kind hereinafter described. Such hydrophile colloids have been claimed for use in resolving naturally-occurring oil-in-water-class crude petroleum emulsions by Blair and Rogers, U. S. Patent No. 2,159,313, issued May 23, 1939, which states:

"We have discovered that these unique emulsions having the peculiar characteristics above referred to, can be rapidly separated into their component parts by treating the same with a minimal concentration of a hydrophile colloid of the kind hereinafter described. The efiective hydrophile colloids intended to be used as the treating agent in our process, are those which give rise only to very small electrical effects when adsorbed at interfaces. In general, they are either the weakly ionized, amphoteric or unionized hydrophile colloids, and are further characterized by the fact that they contain a multiplicity of polar groups, such as COOI-I, -CO'OR, ROR, OI-I, -NH2, NRH, NR2, --CONH--, etc. where R is a univalent organic radical. It may happen that all the polar groups which are present in a hydrophile colloid are of the same kind, or they may be of substantially diiferent kinds, or they may be of several varieties which are generically related to each other. Such hydrophile colloids are characterized by the fact that the polar groups are not segregated at a particular point, but are distributed more or less uniformly throughout the molecule, so that their solution or sol contains a body having what appears to be a more or less uniformly hydrated surface, although the chemical structure of the molecule indicates that the hydrated zones must be interrupted oralternated by nonhydrated zones or groups of non-polar or hydrophobe character.

This feature of distributed hydration along with the concomitant property of distributed hydrophobe characteristics, distinguishes these materials from other hydrophile colloids, such as soaps, the molecules of which are considered as being made up of one defintely polar hydrated end, and one definitely non-polar, non-hydrated end. Inasmuch as these hydrophile colloids contain more than one polar group. they may be referred to as multipolar and may be defined as the multipolar, substantially un-ionized type of hydrophile colloid. The expression substantially un-ionized, as herein used, as intended to include the previously described hydrophile colloids which give rise to minimal electrical effects.

The colloidal dispersions of these hydrophile colloids are relatively non-sensitive to electrolytes, and they often form gels or very viscous, aqueous dispersions. Materials such as soaps, highly ionized dyes, and other relatively strong colloidal electrolytes, high molecular weight organic sulfates and sulfonates, are not included in this classification. Examples of materials having the properties which make them suitable for use as a demulsifying agent for breaking the peculiar oil-in-water type emulsion previously described are: glue, gelatin, casein, starch, albumin, tannin, dextrin, methyl cellulose, watersoluble ethyl cellulose, Prosopz's juliflora. exudate, gum arabic, many other water-dispersible gums, water-dispersible urea-aldehyde resins, etc. In some instances, a mixture of two or more of such materials or colloids may be more effective than one alone. It is recognized that some of these products, such as starch, glue, or the like, produce degradation products which are similar in colloidal nature to their parent material. Obviously, such degradation products could be used with equal effectiveness. In order to designate only the desired type of hydrophile colloid and to exclude the unsuitable type, we will refer to the type employed as being substantially un-ionized. The expression substantially un-ionized is meant to include the type which is un-ionized or weakly ionized or amphoteric. (Page 1, col. 2, line 23-page 2, col. 1, line 44.)

I specifically incorporate into the present specification the examples of such colloid set out therein, including glue and starch.

Certain electrolytes have been claimed for use in resolving naturally-occurring oil-in-waterclass crude petroleum emulsions by Blair U. S. Patent No. 2,159,312, issued May 23, 1939, from which the following is quoted:

Electrolytes which have been found to be the most effective when used with the hydrophile colloids described above are those containing highly charged or relatively highly adsorbable cations, and may be either inorganic or organic compounds. In some cases, compounds containing cations such as Na+ or H+, bearing only one charge, when added to the emulsion described, along with a hydrophile colloid, have been found to give faster and cleaner separation of phases than can be obtained with a hydrophile colloid alone. However, among inorganic elec-. trolytes, it has been found that compounds con- 18 taining divalent, trivalent, tetravalent or higher valence cations, usually .are the most efiective. Organic compounds containing a large highlyadsorbable cation, usually are quite effective in this mixture, regardless of valence.

Examples of electrolytes which I have found to be suitable for admixture with a hydrophile colloid of the kind previously described are: NaCl, KCl, HCl, H2SO4, HNO3, CaClz, MgClz, Ca(NO3)2, FeClz, Th(NO3)4, Ce(SO4)2, IvIg(NO3)2, MgSOi, A12(SO4) 3, AlCls, FeSO4, Fe(NO3).a, methylene blue, fuchsin, many other basic dyes, perlargonidin chloride, cetyl pyridinium bromide, toluidine hydrochloride, diphenyl guanidine hydrochloride, benzyl pyridinium chloride, many other water.- soluble salts of strong or relatively. strong organic bases of moderately high molecular weight, etc. Because of their low cost and avai1ability,.salts of alkaline earth metals and, of iron, such .as

02012, MgCh, MgSO4, BaClz, .and .FeS04, are usually employed. (Page 2, col. 1, line 156-0012, line 14.)

I specifically incorporate into the present specification all the examples of such electrolyte set out therein, including salts of alkaline earth metals, such as calcium chloride.

So far as my experience goes, the proportion of hydrophile colloid, as compared .With thatof poly-amino-poly-halogenated reactionproduct is more important in determining optimum effectiveness on any given emulsion, than is the proportion .of electrolyte employed. In at leastsome instances, the latter appears to be most useful in determining the physical characteristics of the finished mixture, 1. e., desirable fluidity may be achieved by incorporatingsuch electrolyte.

If desired, more than one member of each of my three classes of ingredients may be present in my reagents.

Because of the variability of oil-.in-water-class emulsions on which my reagents are effective, it is impossible to give a single proportionofingredients which will be most-effective on all. As a generalization, I can state that a minimum of 10% of each class of ingredient is desirable,-in the active matter present in my final ternary mixture of poly-amino-poly-halogenated reaction product, colloid, and electrolyte. In other words, not more than of the active matter of my reagent should consist of any one classof ingredient. In general, also, I have found that the most effective proportion, electrolyte-to-colloid,,is usually about 3:1 or 4:1; and the most efiective proportion of poly-amino-poly-halogenated reaction product is commonly about half the .total active matter present in thefinished reagent.

My reagents may contain any desirable solvent. Water is commonly found to be a highly satisfactory solvent, not only because of its ready availability and negligiblecost, but also because it is an excellent solvent for thecolloid andelectrolyte ingredients of my reagents. Non-aqueous liquids may be incorporated into the reagents to the extent that they are-compatible with the. several active-matter ingredients. For example, organic preservatives of the nature of cresols may be added to prevent putrefaction or decomposition of glue, if the latteris used as in ingredient. Other preservatives, such as methyl salicylate, may be incorporated into the reagents, if required or desired. Usually, my reagents exhibit solubilities ranging from rather modest water-dispersibility to full and complete.dispersibilityinthat solvent. Because of the small proportionsused in practising my process, solubility in bulk jhas little significance. In the extremely low concentrations of use they undoubtedly exhibit appre- DEMU'LSIFIER Example 1 DEMULSIFIER Example 2 Mix 3 pounds of corn starch, pounds of calcium chloride, 5 pounds of zinc chloride, 5 pounds of animal glue, 20 pounds of the polyamino-poly-halogenated reaction product of Reaction Product, Example 5, above, and a total of 57 pounds of water, using the calcium chloride as a 50% aqueous solution, the zinc chloride and the glue as 25% aqueous solutions. The mixture was an efiective oil-in-water demulsifier.

DEMULSIFIER Example 3 Mix 5 pounds of animal glue, pounds of calcium chloride, pounds of the poly-amino-poly halogenated reaction product of Reaction Product, Example 8, above, and a total of 60 pounds of water. The glue was used as a aqueous solution, the calcium chloride as a 50% aqueous solution. The mixture was an effective oil-inwater demulsifier.

DEMULSIFIER Example 4 Mix 5 pounds of animal glue, 15 pounds of calcium chloride, 10 pounds each of the poly-aminopoly-halogenated reaction product of Reaction Product, Examples 6 and 18, above, and a total of 60 pounds of water. The glue was used as a 25% aqueous solution, the calcium chloride as a 50 -70 aqueous solution. The mixture was an ef'ective oil-in-water demulsifier.

DEMULSIFIER Example 5 Mix 5 pounds of animal glue, 12.5 pounds of calcium chloride, 20 pounds of the poly-aminopoly-halogenated reaction product of Reaction Product, Example 13, above, and a total of 62.5 pounds of water. The glue was used as a 25% aqueous solution, the calcium chloride as a 50% aqueous solution. The mixture was an effective oil-in-water demulsifier.

DEMULSIFIER Example 6 Mix 5 pounds of animal glue, 20 pounds of calcium chloride, 20 pounds of the poly-amino-polyhalogenated reaction product of Reaction Product, Example 17, above, and a total of 55 pounds of water. The glue was used as a 25% aqueous solution, the calcium chloride as a 50% aqueous solution. The mixture was an effective oil-inwater demulsifier.

DEMULSIFIER Example 7 Mix 5 pounds of animal glue, 15 pounds of calcium chloride, 16.5 pounds of the poly-aminopoly-halogenated reaction product of Reaction Product, Example 9, above, and a total of 79.5 pounds of water. The glue and the calcium chloride were dissolved in 63 pounds of water. The reaction product, 16.5 pounds, was dissolved in 16.5 pounds of water; and the solution was then added to the glue-calcium chloride solution. The mixture was an effective oil-in-water demulsifier.

DEMULSIFIER Example 8 Prepare a reaction product from 400 pounds of the product prepared by heating oxyethylated triisopropanolamine at 250 C. for 10 hours, as in Poly-Amino Reactant, Example 5, and pounds of dichloroisopropyl ether, by heating the two reactants at C. or slightly less until 40% conversion of the chlorine has been achieved, as determined by titration with silver nitrate.

Mix 20 pounds of this reaction product, 20 pounds of a 25% aqueous solution of animal glue, 30 pounds of a 50% aqueous calcium chloride solution, and 30 pounds of water. The total water content of this mixture is 60 pounds. The mixture is an effective oil-in-water demulsifier.

DEMULSIFIER Example 9 Polymerize 56 pounds of cyclohexyldiethanolamine by heating at 255 C. for 20 hours. React 40 pounds of the poly-amino product with 10 pounds of dichloropentanes at about C. until approximately 70% of the chlorine has been converted to the ionic state.

Mix 30 pounds of the above reaction product with 5 pounds of starch, 20 pounds of magnesium sulfate, and 45 pounds of water. The mixture is an effective oil-in-water demulsifier.

DEMULSIFIER Example 10 Heat together 2 moles of triethanolamine and 1 mole of glycerol at 250 C. for 24 hours. The product is a hydroxylated poly-amine. React 30 pounds of this product and 10 pounds of triglycol dichloride at about 110-l20 C. until conversion of approximately 50% of the chlorine has been achieved, as measured by titration with silver nitrate.

Mix 25 pounds of the above reaction product, 7 pounds of animal glue, 20 pounds of calcium chloride, and 48 pounds of water, The mixture is an efiective oil-in-water demulsifier.

'The present reagents are useful, because they are able to recover the oil from oil-in-water class emulsions more advantageously and at lower cost than is possible using other reagents or other processes. In some instances, they have been found to resolve emulsions which were not economically or efiectively resolvable by any other known means.

My reagents may be employed alone, or they may in some instances be employed to advantage admixed with other and compatible oil-in-water demulsifiers.

My process is commonly practised simplyby introducing small proportions of my reagent into an oil-in-water-class emulsion, agitating to secure distribution of the reagent and incipient coalecence, and letting stand until the oil phase separates. The proportion of reagent required will vary with the character of the emulsion to be resolved. Ordinarily, proportions of reagent required are from V to /5 0, the volume of emulsion treated; but more is sometimes required.

I have found that thefactors, reagent feed rate, agitation, and settling time are somewhat interrelated. For example, I havefound that if suflicient agitation of proper character is employed, the settling time is shortened materially. On the other hand, if satisfactory agitation is not available, but extended settling time is, the process is equally productive of satisfactory results.

Agitation may be achieved by any available means. In many cases, it is sufiicient to introduce the reagent into the emulsion and use the agitation produced as the latter flows through a conduit or pipe. In some cases, agitation and mixing are achieved by stirring together or shaking together the emulsion and reagent. In some instances, distinctly improved results are obtained by the use of air or other gaseous medium. Where the volume of gas employed is relatively small and the conditions of its introduction relatively mild, it behaves as a means of securing ordinary agitation. Where aeration is effected by introducing a gas directly under pressure or from porous plates, or by means of aeration cells, the effect is often importantly improved, until it constitutes a difference in kind rather than degree. A sub-aeration type flotation cell, of the kind commonly employed in ore beneficiation operations, is an extremely useful adjunct in the application of my reagents to many emulsions. It frequently accelerates the separation of the emulsion, reduces reagent requirements, or produces an improved effluent. Sometimes all three improvements are cbservable.

Heat is ordinarily of little importance in resolving oil-in-water-class emulsions with my reagents. Still there are some instances where heat is a useful adjunct. This is especially true where the viscosity of the continuous phase of the emulsion is appreciably higher than that ofv water.

In some instances, importantly improved results are obtained by adjusting the pH of the emulsion to be treated, to an experimentally determined optimum value.

The reagent feed rate also has an optimum range, which is sufficiently wide, however, to meet the tolerances required for the variances encountered daily in commercial operations. A large excess of reagent can produce distinctly unfavorable results.

The manner of practising the present invention is clear from the foregoing description. However, for completeness the following specific example is included. The oil-in-water-class emulsion in question was being produced from an oil well. It contained about 1,500 parts-permillion of crude oil, on the average, and was stable for days in absence of any attempt to resolve it; My process was practised at this location by flowing the well fluids, consisting of free crude oil, oil-in-water emulsion, and natural gas, through a gas separator, then to a steel tank of 5,000-barrel capacity. In this tank, the oil-inwater emulsion fellto the bottom and was so separated from the free oil. The oll-in-water emulsion was withdrawn from the bottom of this tank, and the reagent of Demulsifier, Example 9, above, was introduced into the stream at this point. The proportion employed was about 4 the volume of emulsion, on the average. The chemicalized emulsion flowed to a second tank, mixing being achieved in the pipe. In the second tank it was allowed to stand quiescent. Clear water was withdrawn from the bottom of this tank, separated oil from the top.

As an example of the application of the aeration step in my process, the following may be recited: The emulsion was a naturally-occurring petroleum oil-in-water emulsion. It was placed in a sub-aeration flotation cell of the type commonly employed in the ore beneficiation industry. The stirring mechanism was started to begin introduction of the air, and at the same time the mixture of Demulsifier, Example 1, above, was added, the proportion of demulsifier to emulsion being 1150,000. Samples were taken from the bottom of the machine at 1-minute intervals, to follow the progress of the resolution process. At the same time the machine was started, a sample of the same emulsion was placed in a bottle, the same proportion, 1:50,000, of the same reagent was added, the bottle was shaken times, and set down beside the flotation cell. At the end of 5 minutes the water withdrawn from the bottom of the cell was brilliantly clear, whereas the bottle of treated emulsion was still quite opalescent, although some oil separation was observed. The next morning the water in the bottle was substantially as clear as that withdrawn from the cell after 5 minutes. This example illustrates the beneficial influence of the aeration technique. In most cases, it accelerates separation. In some, it permits use of smaller proportions of reagent; but in some cases, it achieves resolution, whereas, in absence of its use, satisfactory separation is not achievable in reasonable time with reasonable reagent consumption.

My reagents have likewise been successfully applied to other oil-in-water-class emulsions, of which representative examples have been referred to above. Their use is therefore not limited to crude petroleum-in-water emulsions.

Having thus described my invention, what I' claim as new and desire to secure by Letters Patent is:

1. A process for breaking emulsions composed of an oil dispersed in a non-oily continuous phase, in which the dispersed phase is not greater than 20%, characterized by subjecting the emulsion to the action of a mixture including (A) a reaction product produced by the reaction between a poly-halogenated non-ionized organic compound in which the halogen atoms are not attached directly to an aromatic ring and a surface-active condensation polymer of mean molecular weight not in excess of 2,000, which latter is in turn obtained by the heat-polymerization of a tertiary aminoalcohol of the formula:

nonmommln in which formula, OR is an alkylene oxide radical having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals, glycide radicals, and methylglycide radicals; R1 is a non-aromatic hydrocarnon radical having 6 carbon atoms or less; m represents a number varying from to 3; n represents the numeral 1, 2, or 3; and n represents the numeral 0, 1, or 2, with the proviso that n+n'=3; (B) a multi-polar, substantially unionizedcolloid of distributed hydrophile character; and (C) a soluble metallic salt, the total active matter of such reagent including at least of each class of ingredient.

2. A process for breaking oil-in-water emulsions, in which the dispersed phase is not greater than characterized by subjecting the emulsion to the action of a mixture including (A) a reaction product produced by the reaction between a poly-halogenated non-ionized organic compound in which the halogen atoms are not attached directly to an aromatic ring and a surface-active condensation polymer of mean molecular weight not in excess of 2,000, which latter is in turn obtained by the heat-polymerization of a tertiary aminoalcohol or" the formula:

[HOR.(OR)m]n \N V lln' in which formula, OR is an alkylene oxide radical having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals, glycide radicals, and methylglycide radicals; R1 is a non-aromatic hydrocarbon radical having 6 carbon atoms or less; m represents a number varying from 0 to 3; n represents the numeral 1, 2, or 3; and n represents the numeral 0, 1, or 2, with the proviso that n+n=3; (B) a multi-polar, substantially un-ionized colloid of distributed hydrophile character; and (C) a soluble metallic salt, the total active matter of such reagent including at least 10% of each class of ingredient.

3. A process for breaking oil-in-water emulsions, in which the dispersed phase is not greater than 1%, characterized by subjecting the emulsion to the action of a mixture including (A) a reaction product produced by the reaction between a poly-halogenated non-ionized organic compound in which the halogen atoms are not attached directly to an aromatic ring and a surface-active condensation polymer of mean molecular weight not in excess of 2,000, which latter is in turn obtained by the heat-polymerization of a tertiary aminoalcohol of the formula:

[HOR.(OR)m]n\ in which formula, OR is an alkylene oxide radical having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals, glycide radicals and methylglycide radicals; R1 is a non-aromatic hydrocarbon radical having 6 carbon atoms or less; 171. represents a number varying from 0 to 3; n represents the numeral 1, 2, or 3; and n represents the numeral 0, l, or 2, with the proviso that n+n'=3; (B) a multi-polar, substantially un-ionized colloid of distributed hydrophile character; and (C) a soluble metallic salt, the total active matter of such reagent including at least 10% of each class of ingredient.

4. A process for breaking petroleum oil-inwater emulsions, in which the dispersed phase is not greater than 1%, characterized by subjecting the emulsion to the action of a mixture including: (A) a reaction product produced by'the reaction between a poly-halogenated un-ionized organic compound in which the halogen atoms are not attached directly to an aromatic ring and a surface-active condensation polymer of mean molecular weight not in excess of 2,000, which latter is in turn obtained by the heat-polymerization of a tertiary aminoalcohol of the formula:

in which formula, OR is an alkylene oxide radical having not more than 4 carbon atoms and. selected from the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals, glycide radicals, and methylglycide radicals; R1 is a non-aromatic hydrocarbon radical having 6 carbon atoms or less; in represents a number Varying from 0 to 3; n represents the numeral 1, 2, or 3; and 11." represents the numeral 0, 1, or 2, with the proviso that n+n'=3; (B) a multi-polar, substantailly unionized colloid of distributed hydrophile character; and (C) a soluble metallic salt, the total active matter of such reagent including at least 10% of each class of ingredient.

5. The process of claim 4, wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2,000.

6. The process of claim 4, wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2,000 and the soluble metallic salt is derived from a polyvalent metal.

'7. The process of claim 4, wherein the heat polymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2,000 and the soluble metallic salt is derived from an alkaline earth metal.

8. The process of claim 1, wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2,000, the hydrophile colloid is a member selected of the class consisting of carbohydrates, proteins, and the naturally-occurring gums, and the soluble metallic salt is derived from an alkaline earth metal.

9., The process of claim 4, wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2,000, the hydrophile colloid is glue, and the soluble metallic salt is derived from an alkaline earth metal.

10., The process of claim 4, wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2,000, the poly-halogenated reactant is chloroform, the hydrophile colloid is glue, and the soluble metallic salt is derived from an alkaline earth metal.

11. The process of claim 4, wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2;000, the poly-halogenated reactant is dichloroethyl ether, the hydrophile colloid is glue, and the'soluble metallic salt is derived from an alkaline earth metal.

12. The process of claim 4, wherein the heatpolymerized aminoalcohol reactant is a heat- 25 polymerized commercial triethanolamine of mean molecular weight not in excess of 2,000, the poly-halogenated reactant is chlorinated paraffin, the hydrophile colloid is glue, and the soluble metallic salt is derived from an alkaline earth metal.

13. A process for breaking emulsions composed of an oil dispersed in a non-oily continuous phase, in which the dispersed phase is not greater than 20%, characterized by subjecting the emulsion to aeration and to the action of a mixture including (A) a reaction product produced by the reaction between a poly-halogenated non-ionized organic compound in which the halogen atoms are not attached directly to an aromatic ring and a surface-active condensation polymer of mean molecular weight not in excess of 2,000, which latter is in turn obtained by the heatpolymerization of a tertiary aminoalcohol of the formula:

[HOR. R)...]..

N iln in Which formula, OR is an alkylene oxide radical having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals, glycide radicals, and methylglycide radicals; R1 is a non-aromatic hydrocarbon radical having 6 carbon atoms or less; m represents a number varying from 0 to 3; n represents the numeral 1, 2, or 3; and n represents the numeral 0, 1, or 2, with the proviso that n+n'=3; (B) a multi-polar, substantially un-ionized colloid of distributed hydrophile character; and (C) a soluble metallic salt, the total active matter of such reagent including at least of each class of ingredient.

14. A process for breaking oil-in-water emulsions, in which the dispersed phase is not greater than characterized by subjecting the emulsion to aeration and to the action of a mixture including (A) a reaction product produced by the reaction between a poly-halogenated non-ionized organic compound in which the halogen atoms are not attached directly to an aromatic ring and a surface-active condensation polymer of mean molecular weight not in excess of 2,000, which latter is in turn obtained by the heat-polymerization of a tertiary aminoalcohol of the formula:

in which formula, OR. is an alkylene oxide radical having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals, glycide radicals, and methylglycide radicals; R1 is a non-aromatic hydrocarbon radical having 6 carbon atoms or less; m represents a number varying from 0 to 3; n represents the numeral 1, 2, or 3; and n represents the numeral 0, 1, or 2, with the proviso that n+n=3; (B) a multi-polar, substantially un-ionized colloid of distributed hydrophile character; and (C) a soluble metallic salt, the total active matter of such reagent including at least 10% of each class of ingredient.

15. A process for breaking oil-in-water emulsions, in which the dispersed phase is not greater than 1%, characterized by subjecting the emulsion to aeration and to the action of a mixture including (A) a reaction product produced by the reaction between a poly-halogenated nonionized organic compound in which the halogen atoms are not attached directly to an aromatic ring and a surface-active condensation polymer of mean molecular weight not inexcess of 2,000, which latter is in turn obtained by the heatpolymerization of .a tertiary aminoalcohol of the formula:

in which formula, OR is an alkylene oxide radical having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals, glycide radicals, and methylglycide radicals; R1 is a non-aromatic hydrocarbon radical having 6 carbon atoms or less; m represents a number varying from 0 to 3; n represents the numeral 1, 2, or 3; and n represents the numeral 0, 1, or 2, with the proviso that n+n'=3; (B) a multi-polar, substantially unionized colloid of distributed hydrophile character; and (C) a soluble metallic salt, the total active matter of such reagent including at least 10% of each class of ingredient.

16. A process for breaking petroleum oil-in- Water emulsions, in which the dispersed phase is not greater than 1%, characterized by subjecting the emulsion to aeration and to the action of a mixture including (A) a reaction product produced by the reaction between a polyehalogenated non-ionized organic compound in which the halogen atoms are not attached directly to an aromatic ring and a surface-active condensation polymer of mean molecular weight not in excess of 2,000, which latter is in turn obtained by the heat-polymerization of a tertiary aminoalcohol of the formula:

in which formula, OR is an alkylene oxide radical having not more that 4 carbon atoms and selected from the class consisting of ethylene oxide radicals, propylene oxide radicals, butylene oxide radicals, glycide radicals, and methylglycide radicals; R1 is a non-aromatic hydrocarbon radical having 6 carbon atoms or less; m represents a number varying from 0 to 3; n represents the numeral 1, 2, or 3; and n represents the numeral 0, 1, or 2, with the proviso that n+n'=3; (B) a multi-polar, substantially un-iom'zed colloid of distributed hydrophile character; and (C) a soluble metallic salt, the total active matter of such reagent including at least 10% of each class of ingredient.

17. The process of claim 16, wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2,000.

18. The process of claim 16, wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2,000 and the soluble metallic salt is derived from a polyvalent metal.

19. The process of claim 16, wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2,000 and the 27 soluble metallic salt is derived from an alkaline earth metal.

20. The process of claim 16, wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2,000, the

' hydrophile colloid is a member selected from the class consisting of carbohydrates, proteins, and the naturally-occurring gums, and the soluble metallic salt is derived from an alkaline earth metal.

21. The process of claim 16, wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2,000, the hydrophile colloid is glue, and the soluble metal- 110 salt is derived from an alkaline earth metal.

22. The process of claim 16, wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2,000, the poly-halogenated reactant is chloroform, the hydrophile colloid is glue, and the soluble metallic salt is derived from an alkaline earth metal.

23. The process of claim 16, wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular weight not in excess of 2,000, the polyhalogenated reactant is chlorinated paraflin, the hydrophile colloid is glue, and the soluble metallic salt is derived from an alkaline earth metal.

24. The process of claim 16 wherein the heatpolymerized aminoalcohol reactant is a heatpolymerized commercial triethanolamine of mean molecular Weight not in excess of 2,000, the poly-halogenated reactant is dichloroethyl ether, the hydrophile colloid is glue, and the soluble metallic salt is derived from an alkaline earth metal.

LOUIS T. MONSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,159,312 Blair May 23, 1939 2,159,313 Blair et al. May 23, 1939 2,407,895 Monson et al Sept. 1'7, 1946 2,470,829 Monson May 24, 1949 

1. A PROCESS FOR BREAKING EMULSIONS COMPOSED OF AN OIL DISPERSED IN A NON-OILY CONTINUOUS PHASE, IN WHICH THE DISPERSED PHASE IS NOT GREATER THAN 20%, CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A MIXTURE INCULDING (A) A REACTION PRODUCT PRODUCED BY THE REACTION BETWEEN A POLY-HALOGENATED NON-IONIZED ORGANIC COMPOUND IN WHICH THE HALOGEN ATOMS ARE NOT ATTACHED DIRECTLY TO AN AROMATIC RING AND A SURFACE-ACTIVE CONDENSATION POLYMER OF MEAN MOLECULAR WEIGHT NOT IN EXCESS OF 2,000, WHICH LATTER IS IN TURN OBTAINED BY THE HEAT-POLYMERIZATION OF A TERTIARY AMINOALCHOL OF THE FORMULA: 